A preferred product has the general formula III 
where, R1 may be the same as or different to R1xe2x80x2, which may be the same as or different to R2, which may be the same as or different to R2xe2x80x2 and is a hydrogen atom or CH3, CH3CH2, xe2x80x94OCH3, xe2x80x94OCH2CH3, xe2x80x94CH2OCH3, xe2x80x94CH2OCH2CH2OCH3, methoxyethoxyethoxymethyl, aryloxymethyl, phenyl, Cl, Br, CN or NO2, xe2x80x94CH2COOR or xe2x80x94CH2NHCORxe2x80x2xe2x80x3 (where Rxe2x80x2xe2x80x3 is C1-C6 alkyl or a phenyl or biphenyl group), or a C1-C5 alkyl group, or an aryl group e.g. a benzyl group, or an xe2x80x94SO3H group or a hydroxyl group or a C1-C5 alkoxy group or an H2PO3 group, and R1 and R1xe2x80x2 are different to R2 and R2xe2x80x2 and n is an integer ranging from 10 to 100.
The present invention relates to polymerisation products of anthraquinone (AQ) with diamino anthracenes (DAA) and to their production. In particular, the invention relates to homopolymers or co-polymers of anthraquinone with 9,10 diaminoanthracene. The polymerisation products may be polymers or oligomers (e.g. of 2 to 12 or 15 repeat units) and the processes of the present invention enables homopolymers and co-polymers to be made which differ only in the substituents which are attached to the anthracene backbone. The co-polymers can be expected on reduction to produce materials which are electroconductive and fairly soluble in a range of commercially viable and environmentally friendly organic solvents. They may also be sufficiently transparent to be used in thin film applications where they may be used as transparent coatings, used extensively in displays, e.g. electroluminescent and liquid crystal displays and to some extent in electromagnetic shielding windows. The copolymers disclosed herein can be used in antistatic applications.
Polymers of aniline and applications thereof have been known for many years. Poly (1-aminoanthracene) (P1-AA hereafter) has also been described recently (Takakazu Yamamoto et al., Macromolecules, 1993, 26, pages 6992-6997). These polymers have similar structures to poly(aniline) and are dark coloured, varying from bluish-black, brown to brown-black powders. Yamamoto states P1-AA has conductivity of the order of 1xc3x9710xe2x88x924 S cmxe2x88x921. P1-AA is stated by Yamamoto to be soluble in organic solvents such as HCOOH, DMF, DMSO and NMP, slightly soluble in CHCl3 and THF, and insoluble in CH3OH, C2H5OH, CH3CN, benzene and toluene. Yamamoto gives no indication of the transparency of P1-AA. The applicants are also aware of two articles namely A. Everaerts et al., Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 24 (7) pp 1703-16 (1986)(hereafter Everaerts) and P. A. Williams et al, Macromolecules 26 (21) pp5820-1 (1993) (hereafter Williams)
The present inventors have been seeking to develop a conductive polymer of sufficient transparency to enable it to be used where light transmission as well as conductivity is required, and in addition solubility which would facilitate fabrication into useful structures, such as films, by solvent methods. In contrast to P1-AA we have discovered surprisingly that certain polymerisation products of anthraquinone with 9,10 diaminoanthracene are sufficiently transparent and soluble electroconductive polymers.
These products may exhibit a particular advantage over the transparent Indium Tin Oxide (ITO) films currently employed in transparent coatings. The ITO coatings lose most or all of their electroconductivity if the surface is bent. However, the products according to the present invention can be expected to maintain their electroconductivity even when bent.
In addition the present inventors wished to devise a procedure by which polymers could be provided in which the polymer backbone was constant and maximum flexibility was provided for varying the substitution on the backbone.
According to one aspect of the present invention, there is provided a polymeric or oligomeric product obtainable from the reaction of an anthraquinone with an aromatic diamine, characterised in that the anthraquinone is substituted or is not substituted and in that the diamine is a diamino anthracene which is substituted or is not substituted. These are preferably produced by polycondensation.
The substitution may be such that the product is a homopolymer or homo-oligomer, or the substitution may be such that the product is a co-polymer or a co-oligomer.
The diaminoanthracene is preferably a 9,10-diaminoanthracene, which may be substituted or not.
The DAA may be substituted with a single substituent e.g. a C1-C5 alkyl, an aryl e.g. a benzyl group, an xe2x80x94SO3H, or xe2x80x94OH, or C1-C5 alkoxy, or aryloxy, e.g. phenoxy or substituted phenoxy or biphenyloxy group or an H2PO3 group or with more than one substituent.
The invention also extends to products in which the anthraquinone is replaced wholly or in part by one or more substituted anthraquinones. Commercially available substituted anthraquinones include:
1-methylaminoanthraquinone;
2-aminoanthraquinone;
1-aminoanthraquinone;
9,10-Anthraquinone-2-sulphonic acid sodium salt;
9,10-Anthraquinone-1,5-disulphonic acid disodium salt;
1-chloroanthraquinone
2-Methylanthraquinone;
2-Ethylanthraquinone;
9,10-Anthraquinone-2,6-disulphonic acid disodiun salt;
2-(Hydroxymethyl)anthraquinone;
Anthraquinone-2-carboxylic acid, (contains 98% 9,10-dihydro-9,10-dioxo-2-anthracenecarboxylic acid)
1,5 dihydroxyanthraquinone;
1,4 dihydroxyanthraquinone;
1,4-Bis(methylamino)anthraquinone;
Benz[a]anthracene-7,12-dione;
1,4-Diaminoanthraquinone;
1,5-Dichloroanthraquinone;
1,5-Dinitro-9,10-anthraquinone;
2,3,6,7-Tetramethyl-anthraquinone;
1-Hydroxy-4-(paratoluidine)anthraquinone;
1-Alkyloxy-3-methoxymethoxy-anthraquinone;
2,6-Di-tert-butyl-anthraquinone;
1-Amino-2-bromo-4-p-tolylamino-anthraquinone;
1-Hydroxy-2-pent-2-enyl-anthraquinone;
1-Amino-4-hydroxy-anthraquinone;
2-[(2-Amino-ethylamino)-methyl]-anthraquinone, dihydrobromide;
1,4-Dimethyl-anthraquinone;
1,4-Diamino-2,3-bis-phenoxy-anthraquinone;
2,7-Dimethyl-anthraquinone;
1,2-Dimethyl-anthraquinone;
1-Iodo-2-methyl-anthraquinone;
The ratio of anthraquinone to aromatic diamine is in the range preferably of 5:1 to 1:5, eg. in the range 3:1 to 1:3, more preferably in the range 2:1 to 1:2, e.g. 1:1. Preferably the anthraquinone is a C1-C6 alkyl anthraquinone or a C1-C10 alkoxy anthraquinone or a hydroxyanthraquinone, for example the anthraquinone may be 2-ethyl anthraquinone or 2-methyl anthraquinone, or 2,3-dimethyl anthraquinone or 2,6-dioctyloxy anthraquinone or 2,6-dihydroxyanthraquinone.
The diaminoanthrance may be substituted in the same way as the anthraquinone and with the same range of substituents.
Preferred substituted anthraquinones are C1-C6 alkyl anthraquinones e.g. 2-ethyl anthraquinone or 2-methyl anthraquinone, or 2,3-dimethyl anthraquinone or C1-C10 alkoxy anthraquinones e.g. 2,6-dioctyloxy anthraquinone or hydroxyanthraquinones e.g. 2,6-dihydroxyanthraquinone.
More broadly, the substituted anthraquinones may be of general formula (1): 
where, R may be the same as or different to Rxe2x80x2, and may be a hydrogen atom (when R=Rxe2x80x2=H, the compound is anthraquinone), or CH3, CH3CH2xe2x80x94, xe2x80x94OCH3, xe2x80x94OCH2CH3, xe2x80x94CH2OCH3, xe2x80x94CH2OCH2CH2OCH3, methoxyethoxyethoxymethyl, aryloxymethyl, phenyl, Cl, CN or NO2, xe2x80x94CH2COOR or xe2x80x94CH2NHCORxe2x80x3 (where Rxe2x80x3 is C1-C6 alkyl or a phenyl or biphenyl group).
The invention also extends to polymeric products having the general formula 
where, R1 may be the same as or different to Rxe2x80x2, which may be the same as or different to R2, which may be the same as or different to R2xe2x80x2, and each of R1,R1xe2x80x2,R2 and R2xe2x80x2 may be a hydrogen atom or CH3, CH3CH2xe2x80x94, xe2x80x94OCH3, xe2x80x94OCH2CH3, xe2x80x94CH2OCH3, xe2x80x94CH2OCH2CH2OCH3, methoxyethoxyethoxymethyl, aryloxymethyl, phenyl, Cl, CN or NO2, xe2x80x94CH2COOR or xe2x80x94CH2NHCORxe2x80x2xe2x80x3 (where Rxe2x80x2xe2x80x3 is C1-C6 alkyl or a phenyl or biphenyl group), or a C1-C5 alkyl group, or an aryl group e.g. a benzyl group, or an xe2x80x94SO3H group or a hydroxyl group or a C1-C5 alkoxy group or an H2PO3 group, and R1 and R1xe2x80x2 are different to R2 and R2xe2x80x2 and n is an integer ranging from 2 to 100 preferably from 10 to 100, preferably 50 to 80, e.g. about 70.
The invention also extends to polymeric products having the general formula (II) 
where, R1 may be the same as or different to R1xe2x80x2, and each of R1 and R1xe2x80x2 is a hydrogen atom or CH3, CH3CH2, xe2x80x94OCH3, xe2x80x94OCH2CH3, xe2x80x94CH2OCH3, xe2x80x94CH2OCH2CH2OCH3, methoxyethoxyethoxymethyl, aryloxymethyl, phenyl, Cl, CN or NO2, xe2x80x94CH2COOR or xe2x80x94CH2NHCORxe2x80x2xe2x80x3 (where Rxe2x80x2xe2x80x3 is C1-C6 alkyl or a phenyl or biphenyl group), and R2 may be the same or different to R2xe2x80x2 and each of R2 and R2xe2x80x2 is a hydrogen atom or a C1-C5 alkyl group, or an aryl group e.g. a benzyl group, or an xe2x80x94SO3H group or a hydroxyl group or a C1-C5 alkoxy group or an H2PO3 group, and R1 and R1xe2x80x2 are different to R2 and R2xe2x80x2 and n is an integer ranging from 2 to 100 preferably from 10 to 100.
In one form of the invention R1 is the same as R1xe2x80x2 but is different from R2 and R2xe2x80x2 and in that R2 and R2xe2x80x2 are the same, i.e. a copolymeric form.
In another form of the invention R1 is the same as R1xe2x80x2 and as R2 and R2xe2x80x2 but is not hydrogen, i.e. a homopolymeric form.
In another form of the invention R1 is different from R1xe2x80x2 and R2 is different from R2xe2x80x2 and R1 and R1xe2x80x2 are both different from R2 and R2xe2x80x2, i.e. a copolymeric form.
In another form of the invention R1 and R2 are not hydrogen and R1xe2x80x2 and R2xe2x80x2 are not the same, i.e. a copolymeric form.
Poly (9-aminoanthracene)s) in accordance with the invention are also provided characterised in that they have an oxidation state between 0.25 to 0.75, and a formula (III) at an oxidation state 0.25, a formula (IV) at an oxidation state 0.5 and a formula (V) at an oxidation state 0.75 as follows 
in which R1 to R8 are not all hydrogen, and R1, R3, R5 and R7 and R1xe2x80x2, R3xe2x80x2, R5xe2x80x2 and R7xe2x80x2 are the same as R1 and R1xe2x80x2 as defined in connection formula (II), and R2, R4, R6 and R8 and R2xe2x80x2, and R4xe2x80x2, and R6xe2x80x2 and R8xe2x80x2 are the same as R2 and R2xe2x80x2 as defined in connection with formula (II) and p is an integer ranging from 10 to 100.
Poly (9-aminoanthracenes) in accordance with the invention are also provided characterised in that they have an oxidation state between 0.25 to 0.75, and a formula (III) at an oxidation state 0.25, a formula (IV) at an oxidation state 0.5 and a formula (V) at an oxidation state 0.75 as follows 
in which the R groups are the same as the Rxe2x80x2 groups and the R groups are all the same; or
the R groups are the same as the Rxe2x80x2 groups and the R1, R3, R5 and R7 groups are all the same and the R2, R4, R6 and R8 groups are all the same but are different to the R1, R3, R5 and R7 groups; or
the R groups are different to the Rxe2x80x2 groups and the R1, R3, R5 and R7 groups are all the same and the R2, R4, R6 and R8 groups are all the same but are different to the R1, R3, R5 and R7 groups, and R1, R3, R5 and R7 and R1xe2x80x2, R3xe2x80x2, R5xe2x80x2 and R7xe2x80x2 are the same as R1 and R1xe2x80x2 as defined in connection formula (II), and R2, R4, R6 and R8 and R2xe2x80x2, and R4xe2x80x2, and R6xe2x80x2 and R8xe2x80x2 are the same as R2 and R2xe2x80x2 as defined in connection with formula (II) and p is an integer ranging from 10 to 100.
Polymers with lower values of p, e.g. 2 to 10, or 2-15 which may be referred to as oligomers, will have higher solubility but may have lower heat stability.
The co-polymers of the invention can be expected on reduction to produce materials which are conductive and therefore may find uses in thin film technology, as EMI, RFI (electro magnetic interference, radio frequency interference) shielding materials and in display systems, such as electroluminescent and liquid crystal display systems as a transparent electrode.
The copolymers disclosed herein can be used even without reduction in antistatic applications.
Such reduced polymeric products may be used with other polymers (or binders). The polymeric productxe2x80x94binder blend may comprise from 5 to 70% by weight of the polymeric product and from 95 to 30% by weight of the other polymer. The polymer with which the polymeric product is blended may be, for example, poly(vinyl chloride), polyethylene, polypropylene, polystyrene, nylon, poly(acrylonitrile-butadiene-styrene), poly(ethylene terephthalate), poly(ethylene oxide), polymethyl methacrylate, polyether sulphone, polyether ketone, polytetrafluoroethylene.
These blends may have sufficient conductivities to give good antistatic properties at the lower concentrations of polymeric product. At the higher concentrations the blends may possess levels of conductivity which may be useful for shielding.
Furthermore, the polymeric product imparts the required electrical property to the blend immediately and unlike alkylammonium salts, do not need moisture to impart conductivity to the polymer.
Conductive adhesives may be formulated using the polymeric product of the present invention.
The polymeric product of the present invention may also be directly deposited chemically or electrochemically onto and/or impregnated into a porous polymer film such as poly(vinyl chloride), poly(carbonate) or poly(propylene). The surface of a component so formed can be permanently conductive and may have good antistatic properties.
This surface may be painted with coloured dyes or pigments and the colour modified without impairing the antistatic properties. This method may enable antistatic floors and mats to be fabricated from the composites.
Furthermore, non-conductive materials such as talc or mica may be coated with the polymeric product of the invention either chemically or electrochemically. Such coated powders may be useful as fillers for the formation of conductive polymer composites.
Furthermore, solutions of the solvent soluble polymeric product may be sprayed onto a non-conducting surface which can then become conductive on evaporation of the solvent therefrom. The resulting film can be used in display devices.
The invention also extends to a method of production of a homopolymer or copolymer or homo-oligomer or co-oligomer product characterised in that the product is obtained by condensation of an anthraquinone, substituted or not with a diaminoanthracene. substituted or not. Thus the polymeric product of the present invention may be prepared by the polycondensation of anthraquinone with DAA e.g. 9,10 diaminoanthracene using a titanium compound as a condensing agent. Examples of suitable titanium compounds include titanium tetrachloride and titanium alkoxides such as titanium tetraisopropoxide and titanium tetra-n-butoxide. Typically, a hindered base is also present in the reaction. Examples of such bases include 1,4-diazabicyclo[2,2,2]octane (Dabco), 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU) and quinuclidine. Lewis acids, such as molybdenum pentachloride, aluminium chloride and ruthenium trichloride, may also be employed.
Preferably the diamino anthracene is dissolved in a suitable solvent and is heated with the titanium compound and a hindered base, the anthraquinone compound is added to the mixture and the mixture is stirred and heated e.g. for a period in excess of 12 hours, the mixture is filtered and the residue is washed and the product is purified.
Preferably the ratio of anthraquinone to DAA is in the range 5:1 to 1:5, more preferably in the range 3:1 to 1:3 and most preferably in the range 2:1 to 1:2, e.g. 1:1.
An alternative reaction procedure is merely to heat the anthraquinone and the DAA together e.g. in the presence of a solvent but in the absence of a catalyst or any other species e.g. used to facilitate condensation. This produces purer species but at lower yields as compared to catalysed reaction systems.
If substituted anthraquinones are used then low yields can be tolerated because one can recover unreacted substituted anthraquinones and moreover DAA by differential solubilisation using different solvents to dissolve out these soluble species e.g. sequentially.
The polymeric products produced may be dissolved in common organic solvents such as chloroform, or tetrahydrofuran and may also be processable into thin films. It is also possible to partially reduce the produced polymeric products with a suitable reducing agent, for example sodium cyanoborohydride, sodium borohydride, sodium borohydride-boron trifluoride etherate, lithium aluminium hydride, hydrazine and dithionites. These partially reduced polymeric products may have a lighter colour and sufficient electroconductivity to be used in transparent thin film technology. It is also possible to dope these polymeric products with suitable acid dopants, for example camphorsulphonic acid, 5-sulphosalicylic acid, para-toluenesulphonic acid, trifluoromethanesulphonic acid (triflic acid), methanesulphonic acid, trifluoroacetic acid, hydrochloric acid and sulphuric acid. This may enhance the electroconductivity of the polymeric product.
The invention also extends to a transparent electroconductive coating or to a static shielding material comprising a product in accordance with the present invention.
The invention also extends to a process which comprises reacting a lithium salt of DAA substituted or not with an anthraquinone substituted or not. In a preferred form of this aspect the invention also extends to a method in which DAA substituted or not is reacted in a solvent under inert gas with an organolithium compound, e.g. n-butyllithium or lithium diisopropyl amide, at low temperature, at which the resulting lithium DAA salt is stable, preferably xe2x88x9270xc2x0 C. or lower, but above the freezing point of the reaction mixture, to produce a DAA lithium salt, the temperature of the reaction mixture is then allowed to rise e.g. to at least xe2x88x9220xc2x0 C., preferably to room temperature and the reaction mixture is then added to anthraquinone, substituted or not, and the reaction allowed to occur, preferably at elevated temperature, e.g. by refluxing, to remove the water produced in the condensation reaction from the reaction mixture.
Lithium diisopropylamide may be used instead of butyllithium because it has the advantage of being a hindered compound as compared to butyl lithium and thus may be expected to have a lesser tendency to react with the carbonyl group of the anthraquinone. If desired the reaction solvent e.g. tetrahydrofuran can be replaced by a higher boiling solvent e.g. diglyme. Preferably such replacement solvent also has the advantage (possessed by diglyme) of forming an azeotropic mixture with water thus facilitating removal of the water formed during the condensation reaction and driving the reaction to higher yields.
The invention also extends to lithium salts of diaminoanthracene whether substituted or not.
In addition to the utility of these materials in the present reaction systems they may have utility as an intermediate or a starting material in other reaction systems.